Isoxazolyl-alkyl thiocarbamates and herbicidal compositions thereof

ABSTRACT

Novel isoxazolyl-alkyl thiolcarbamates and novel herbicidal compositions containing the novel thiolcarbamates are disclosed wherein the thiolcarbamates are of the formula: ##STR1## in which R 1  and R 2  are identical or different and each represents a hydrogen atom, a linear or branched alkyl radical containing 1 to 6 carbon atoms, a cycloalkyl radical containing 3 to 6 carbon atoms, an alkenyl radical containing 2 to 4 carbon atoms, an alkoxy radical containing 1 to 6 carbon atoms, an alkoxyalkyl radical in which each alkyl part contains 1 to 4 carbon atoms, an optionally substituted aryl radical, an optionally substituted aralkyl radical in which the alkyl part contains 1 to 4 carbon atoms, or a saturated or unsaturated heterocyclic radical which has 5 to 6 chain members and contains, as the hetero-atom, an oxygen, nitrogen or sulphur atom, or R 1  and R 2  together with the nitrogen atom to which they are bonded form a saturated or unsaturated, optionally substituted heterocyclic structure which has 5 to 6 chain members and can contain, as a hetero-atom, an oxygen atom in addition to the nitrogen atom, R 3  represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms and Y and Y&#39; are identical or different and each represents a hydrogen or halogen atom, an alkyl radical containing 1 to 6 carbon atoms, a trifluoromethyl radical or an optionally substituted aryl radical. The new thiolcarbamates are useful in the form of herbicidal compositions for the selective destruction of weeds in crops of maize, groundnuts, rape, cotton, soya, beans, sunflowers, wheat and rice.

BACKGROUND OF THE INVENTION

The invention relates to novel isoxazolyl-alkyl thiolcarbamates. It alsorelates to herbicidal compositions containing these compounds and to theprocesses for the selective destruction of weeds by means of thesecompositions.

French Patent Application No. 2,205,514 claims derivatives ofthiolcarbamic acid and of dithiolcarbamic acid which are biodegradableherbicides and are of the general formula: ##STR2## in which: A, B and Care identical or different and represent oxygen, nitrogen or sulphuratoms, --CH-- chain members, or NR₃ radicals (in which R₃ represents ahydrogen atom or an alkyl radical), Z represents an oxygen or sulphuratom, D represents a halogen or an alkyl radical , NO₂ or SR₄ (R₄ =H oralkyl) and R₁ and R₂ are identical or different and represent H or alower alkyl.

This general formula E encompasses a very large number of compoundsbelonging to several different chemical families. The only compoundsdescribed in the examples illustrating this application areimidazolyl-alkyl thiolcarbamates, oxadiazolyl-alkyl-thiolcarbamates andthiazolyl-alkyl thiolcarbamates. Not a single isoxazolyl-alkylthiolcarbamate is described in these examples and, consequently, noindication is given regarding the herbicidal properties of thesecompounds and their selectivity with respect to crops.

SUMMARY OF THE INVENTION

The compounds according to the invention are of the following generalformula: ##STR3## in which: R₁ and R₂ are identical or different andeach represents a hydrogen atom, a linear or branched alkyl radicalcontaining 1 to 6 carbon atoms, a cycloalkyl radical containing 3 to 6carbon atoms, an alkenyl radical containing 2 to 4 carbon atoms, analkoxy radical containing 1 to 6 carbon atoms, an alkoxyalkyl radical inwhich each alkyl part contains 1 to 4 carbon atoms, an optionallysubstituted aryl radical, an optionally substituted aralkyl radical inwhich the alkyl part contains 1 to 4 C, or a saturated or unsaturatedheterocyclic radical which has 5 to 6 chain members and contains, as thehetero-atom an oxygen, nitrogen or sulphur atom, or R₁ and R₂ can alsoform, together with the nitrogen atom to which they are bonded, asaturated or unsaturated, optionally substituted heterocyclic structurewhich has 5 to 8 chain members and can contain, as a hetero-atom, anoxygen atom in addition to the nitrogen atom, R₃ represents a hydrogenatom or an alkyl radical containing 1 to 4 carbon atoms and Y and Y' areidentical or different and each represents a hydrogen or halogen atom,an alkyl radical containing 1 to 6 carbon atoms, a trifluoromethylradical or an optionally substituted aryl radical.

Herbicidal compositions of the invention, which can be used inagriculture, contain as the active material, at least one of thecompounds defined by formula A.

DESCRIPTION OF THE INVENTION

Depending on the position of the alkyl thiolcarbamate radical of anisoxazole ring, the compounds according to the general formula A citedfurther above correspond to one or another of the formulae B, C and Dwhich follow: ##STR4## in which R₁, R₂,R₃, Y and Y' have the samemeaning as in formula A.

The compounds according to the invention generally have an excellentherbicidal activity against graminaceous weeds, such as, for example,wild oats (Avena fatua), crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloa crus-galli) raygrass (Lolium multiflorum), foxtail(Setaria faberii) and slender foxtail (Alopecurus myosuroides). Some ofthe compounds also have a good herbicidal action against dicotyledonousweeds, such as goosefoot (Chenopodium album), nightshade (Solanumnigrum), mustard (Sinapis arvensis) and chickweed (Stellaria media).They can be used for the selective destruction of weeds in crops such asmaize, groundnuts, rape, cotton, soya, sunflowers, wheat, beans and riceand are applied before sowing or before emergence of the crops.

The compounds according to the general formula A are prepared accordingto a process which is analogous to that described in U.S. Pat. No.3,579,525 for preparation of pyridylmethyl thiol- or dithiol-carbamatesbut which is used here for the preparation of isoxazolyl-alkylthiolcarbamates, in accordance with the global reaction equation:##STR5## in which Y, Y', R₁, R₂ and R₃ have thhe same meaning as informula A and X represents a chlorine or bromine atom.

For this purpose, the amine HNR₁ R₂ and carbon oxysulphide are reacted,in a first stage, in the presence of sodium hydroxide in an aqueous oraqueous-organic medium at a temperature of between 0° and 20° C. andpreferably of about 10° C., in order to obtain a sodium thiolcarbamate,and the halogenoalkylisoxazole is then added to the reaction mixture,the reaction being carried out at a temperature of between 0° and 80° C.After stirring for a period of 1 to 4 hours, the reaction mixture isdecanted and the aqueous phase is then extracted with a solvent, suchas, for example, benzene. The organic phase thus obtained is then washedand dried and the solvent is removed by the usual procedures, forexample by evaporation under reduced pressure.

Depending on whether the compound which it is desired to prepare fallsunder formula B, C or D given above, the starting material used is ahalogenoalkyl-isoxazole of one of the following formulae: ##STR6##respectively, in which R₁,R₂, R₃, X, Y and Y' have the same meaning asabove.

The 5-halogenoalkyl-isoxazoles of the formula B' can be prepared byseveral processes which are in themselves known.

According to a first process, the compounds according to the formula B',in which X, Y and R₃ have the same meaning as above and Y' represents ahydrogen atom or an alkyl, trifluoromethyl or optionally substitutedaryl radical, are prepared by the cycloaddition of a nitrile oxide ontoa halogenoalkyne, in accordance with the reaction equation: ##STR7##

This process has been described in Atti Soc peloritana Sci fis mat nat3,179-86 (1956-57) for the preparation of3-phenyl-5-chloromethyl-isoxazole.

Because of the instability of the nitrile oxide, it is preferable toprepare this oxide in situ.

For this purpose, according to a first process which is in itself known,a nitroalkane of the formula Y--CH₂ NO₂ is dehydrated by means of aphenyl isocyanate, in the presence of a tertiary amine, in accordancewith the reaction equation:

    Y--CH.sub.2 NO.sub.2 +2C.sub.6 H.sub.5 --N═C═O→Y-C.tbd.N→O+CO.sub.2 +(C.sub.6 H.sub.5 NH).sub.2 CO

in which Y has the same meaning as above.

This process has been described in J Amer. Chem. Soc. 82 p. 5339 (1960)and also in Belgian Pat. No. 772,490 for the preparation of3-alkyl-5-halogenomethyl-isoxazoles.

The nitrile oxide can also be prepared in situ according to a processwhich is in itself known by reacting a mineral or organic base with achloroaldoxime, in accordance with the reaction equation: ##STR8##

This process has been described in Atti Soc. peloritana Sci fis mat nat3,179-86 (1956-57) for the preparation of3-methyl-5-chloromethyl-isoxazole.

The chloroaldoxime can also be prepared in situ by reacting chlorinewith an aldoxime at a temperature of between -20° C. and +5° C., eitherin an organic solvent medium, for example methylene chloride orpetroleum ether, or in aqueous media, for example in a dilute aqueoussolution of hydrochloric acid.

The 5-halogenoalkyl-isoxazoles of the formula ##STR9## in which Y hasthe same meaning as above and Y' represents a halogen atom, can beobtained directly by halogenation of compounds of the formula ##STR10##according to a method which is in itself known and is described in Rendist lombardo sci 69, 587-601, 1936, for the preparation of5-methyl-4-chloro-isoxazole and of 5-methyl-4-bromo-isoxazole.

The 3-halogenoalkyl-isoxazoles according to formula C' can be preparedby the following processes:

According to a first process, which is in itself known, the compoundsaccording to the formula C', in which X and Y' have the same meaning asabove and Y represents a hydrogen atom or an alkyl, trifluoromethyl oroptionally substituted aryl radical, can be prepared by reacting an acidchloride with an alkyne, and then treating the halogenoalkyl vinylketone thus obtained with a hydroxylamine hydrochloride, in accordancewith the following reaction equation: ##STR11##

The compounds according to the formula C' in which Y is a halogen atomcan be obtained by halogenation of compounds in which Y represents ahydrogen atom, in accordance with the method described by "Rend istlombardo Sci" 69, 587-601, 1936, already cited above.

The 4-halogenoalkyl-isoxazoles of the formula D' can be prepared,according to a process which is in itself known and is described in ZhurObshchei Khim 28 2736-45 (1958) for the preparation of3-methyl-4-chloromethyl-isoxazole, 5-methyl-4-chloromethyl-isoxazole,4-chloromethyl-isoxazole and 5-phenyl-4-chloromethyl-isoxazole.

According to this process, the 4-chloroalkyl-isoxazoles of the formula##STR12## in which R₃, Y and Y' have the same meaning as above, areobtained by the action of paraformaldehyde and hydrochloric acid, in thepresence of ZnCl₂, on an isoxazole of the formula ##STR13##

The 4-bromoalkyl-isoxazoles and 4-iodoalkyl-isoxazoles can be obtainedusing the 4-chloroalkyl-isoxazoles as the starting materials, inaccordance with the process described in Isvest Akad Nauk SSSR OtdelKhim Nauk 1952 87-92.

The examples which follow illustrate the invention without, however,restricting it.

In the text which follows, Example B'₁ to B'₆, C'₁ to C'₂ and D'₁relate, respectively, to the preparation of halogenoalkyl-isoxazoles ofthe general formulae B', C' and D' respectively and Examples 1 to 4relate to the preparation of isoxazolyl-alkyl thiolcarbamates accordingto the invention and to the tests showing the herbicidal activity ofthese compounds.

Preparation of halogenoalkyl-isoxazoles EXAMPLE B'1 Preparation of3-methyl-5-chloromethyl-isoxazole using nitroethane as the startingmaterial

238.0 g (2 mols) of phenyl isocyanate and 82.0 g (1.1 mols) of3-chloro-propyne in 500 ml of benzene are brought to a temperature of85° C. A solution of 75.0 g (1 ml) of nitroethane and 10 ml oftriethylamine in 250 ml of benzene is then run in dropwise. After a fewminutes, a precipitate of urea appears and carbon dioxide gas isevolved. The addition is made at a rate which is just sufficient tomaintain boiling without external heating. Reflux is maintained byheating for one hour after the end of the addition. After cooling, themixture is filtered, the filtrate is concentrated and the residue isdistilled under reduced pressure. This gives: 97.0 g of3-methyl-5-chloromethyl-isoxazole.

Boiling point: 80° C./15 mm Hg. Yield: 73.7%.

EXAMPLE B'2

The following compounds were prepared from suitable starting materialsusing a procedure as in Example B'1:

3-methyl-5-bromomethyl-isoxazole; boiling point 50° C. (0.5 mm Hg)

3-ethyl-5-chloromethyl-isoxazole; boiling point 90° C. (13 mm Hg), n_(D)²⁰ =1.454, and

3-methyl-5-(1-chloroethyl)-isoxazole; boiling point 82° C. (14 mm Hg),n_(D) ²⁵ =1.4755.

EXAMPLE B'3 Preparation of 3-(tertiary butyl)-5-chloromethyl-isoxazole,using pivaldoxime as the starting material

37.8 g (0.37 mol) of pivaldoxime dissolved in 400 ml of methlenechloride are chlorinated with 26.5 g (0.37 mol) of chlorine at atemperature of between -5° C. and 0° C. After stirring for +minutes at0° C., 28 g (0.37 mol) of 3-chloro-propyne are added and 30 g (0.75 mol)of sodium hydroxide dissolved in 200 ml of water are run in, whilststirring vigorously, at a temperature of about 5° C. Stirring iscontinued overnight, the temperature being allowed to rise to ambienttemperature.

The mixture is decanted and the aqueous phase is extracted withmethylene chloride. The combined organic phases are dried and thesolvent is evaporated. The residue is distilled under reduced pressureand this gives: 56.2 g of 3-(tertiary butyl)-5-chloromethyl-isoxazole.

yield=85.5%. Boiling point: 80° C./15 mm Hg.

EXAMPLE B'4

The following compounds were prepared from suitable starting materialsusing a procedure as in Example B'3.

3-methyl-5-chloromethyl-isoxazole; boiling point 86°-89° C. (19 mm Hg),n_(D) ²⁵ =1.4797

3-(n-proply)-5-chloromethyl-isoxazole; boiling point: 110°-112° C. (14mm Hg), n_(D) ²⁵ =1,4744

3-isopropyl-5-chloromethyl-isoxazole; boiling point= 100°-106° C. (15 mmHg), n_(D) ²⁰ =1.4707

3-isopropyl-5-(1-chloroethyl)-isoxazole; boiling point: 102°-106° C. (14mm Hg)

3-phenyl-5-chloromethyl-isoxazole; melting point: 69.2° C., and

3-(2,6-dichlorophenyl)-5-chloromethyl-isoxazole; boiling point:148°-149° C. (0.05 mm Hg), n_(D) ²⁰ =1.5883

EXAMPLE B'5 Preparation of 3-methyl-4-chloro-5-(1-chloroethyl)-isoxazoleby chlorination of 3-methyl-5(1-chloroethyl)-isoxazole

29.1 g (0.2 mol) of 3-methyl-5-(1-chloroethyl)-isoxazole are rundropwise into 54.0 g (0.4 mol) of sulphuryl chloride at abienttemperature. The reaction mixture is left to stand for 48 hours atambient temperature and is then concentrated and distilled under reducedpressure. This gives: 31.0 g of3-methyl-4-chloro-5-(1-chloroethyl)-isoxazole; boiling point=89°-91°C./17 mm Hg.

Yield: 86.1%.

EXAMPLE B'6

the following products were prepared from suitable starting materialsusing a procedure as in Example B'5:

3-methyl-4-chloro-5-chloromethyl-isoxazole; boiling point 83°-84° C./15mm Hg, n_(D) ²⁵ =1.4935

3-methyl-4-bromo-5-bromomethyl-isoxoazole; boiling point 90°-93° C./11mm Hg, melting point: 38° C.

3-ethyl-4-chloro-5-chloromethyl-isoxazole; boiling point: 97°-100° C./17mm Hg, n_(D) ²⁵ :1.4905, and

3-isopropyl-4-chloro-5-(1-chloroethyl)-isoxazole; n_(D) ²⁵ :1.4786

EXAMPLE C'1

113 g (1 mol) of monochloroacetyl chloride are run dropwise into asuspension of 180 g of aluminum chloride in 400 ml of anhydrous ethylenechloride at a temperature below 5° C. A stream of acetylene is thenpassed in, whilst keeping the temperature at between 0° and 10° C., for3 hours 30 minutes.

The reaction mixture is then poured onto 1 kg of ice and 20 ml ofconcentrated hydrochloric acid. After stirring for 30 minutes, themixture is decanted and the aqueous phase is extracted with twice 100 mlof methylene choride. The organic phases are washed successively withwater, with a bicarbonate solution and finally with water, and driedover MgSO₄ after evaporation of the solvents. The residue is distilledunder reduced pressure. This gives 106.1 g of chloromethyl 2-chlorovinylketone (90% trans isomer and 10% cis isomer); yield: 76.3%. Boilingpoint: 74°-79° C./18 mm Hg.

60.0 g (0.43 mol) of chloromethyl chlorovinyl ketone and 30.0 g (0.43mol) of hydroxylamine hydroxylamine dissolved in 300 ml of methanol areheated under reflux for 3 hours. The methanol is then distilled underatmospheric pressure and the residue is taken up in 150 ml of methylenechloride. The aqueous phase which separates out is decanted off andextracted with methylene chloride. After drying over magnesium sulphateand evaporating off the solvent, the residue is distilled under reducedpressure. This gives 40.9 g (yield: 80.7%) of 3-chloromethyl-isoxazole;boiling point: 63°-66° C./19 mm Hg.

EXAMPLE C'2

The following compounds were prepared from suitable starting materialsusing a procedure as indicated in Example C'1;

3-(1-chloroethyl)-isoxazole; boiling point: 67°-68°/21 mm Hg, n_(D) ²⁵:1.4685

3-chloromethyl-5-methyl-isoxazole and

3-(1-chloroethyl)-5-methyl-isoxazole.

EXAMPLE D'1

4-Chloromethyl-3,5-dimethyl-isoxazole was obtained according to thepreparation described in Zhur Obshchei Khim 28 2736-45 1958; boilingpoint: 90°-95° C. under 16 mm Hg.

Preparation of isoxazolyl-alkyl thiolcarbamtes according to theinvention EXAMPLE 1

Preparation of 3-methyl-isoxazol-5-yl-methylN,N-di-(n-propyl)-thiolcarbamate (compound No. 3).

115.2 g (2.88 mols) of sodium hydroxide pellets and 290.9 g (2.88 mols)of di-n-propylamine are dissolved in 2.5 l of water and the solution iscooled to 10° C. using a bath of ice-water. 172.8 g (2.88 mols) ofcarbon oxysulphide are absorbed into this solution with the aid of afinger-shaped glass frit, any gas which may not have been absorbed beingcondensed in a condenser cooled by a mixture of solid carbondioxide/acetone. The reaction mixture is then stirred for 10 minutes at10° C. and 315.6 g (2.4 mols) of 3-methyl-5-chloromethyl-isoxazole arethen added rapidly. The mixture is stirred for 3 hours, the temperaturebeing allowed to rise to ambient temperature, and then decanted and theaqueous phase is extracted with twice 500 ml of benzene and the combinedorganic phases are then washed with water until neutral, dried overmagnesium sulphate, concentrated and distilled under reduced pressure.This gives 526.6 g of 3-methyl-isoxazol-5-yl-methylN,N-di-(n-propyl)-thiolcarbamate. Boiling point=137° C./0.06 mm Hg.Yield: 85.7%. n_(D).sup. 25 =1.5091.

The preparation of 3-methyl-5-chloromethyl-isoxazole which is used asthe starting material has been described in Example B'1.

EXAMPLE 2 Preparation of 3-methyl-isoxazol-5-yl-methylN,N-diiso-propyl-thiolcarbamate (compound No. 10)

120 g (3 mols) of sodium hydroxide and 303 g (3 mols) ofdiisopropylamine are dissolved in 1.5 l of water and the solution iscooled to about 10° C. 135 g (2.25 mols) of carbon oxysulphide areabsorbed by this solution, wit the aid of a finger-shaped glass frit,the gas which has not been absorbed being condensed in a condensercontaining solid carbon dioxide/acetone.

After the reaction mixture has been stirred for 10 minutes at 10° C.,197.2 g (1.5 mols) of 3-methyl-5-chloromethyl-isoxazole are addedrapidly, whilst stirring vigorously. A white precipitate formsimmediately. Stirring is continued for 4 hours, the temperature beingallowed to rise to ambient temperature. The precipitate is then filteredoff and washed with water until neutral and is then dried at 40° C.under reduced pressure. This gives 353.5 g of3-methyl-isoxazol-5-yl-methyl N,N-diisopropyl-thiolcarbamate.

Melting point=67°-68° C.; yield: 92%.

The preparation of 3-methyl-5-chloromethyl-isoxazole, which is thestarting material, has been described in Example B'1.

EXAMPLE 3

Following the procedure of Example 1, compounds 1, 2, 4 to 9 and 11 to70 were prepared starting from suitable starting materials. Thephysico-chemical characteristics of these compounds are given in thetable below.

In this table:

the defining the alkyl radicals have the following meanings:

Me: methyl

Et: ethyl

Pr: normal propyl

iso Pr: isopropyl

Bu: primary normal butyl

sec. Bu: secondary normal butyl

iso-Bu: isobutyl

ter-Bu: tertiary butyl

and the symbol (B), (C) or (D) given below the number of each compoundindicates to which of the formulae B, C and D this compound corresponds.

      (Formula B) Com-  Molec-   pound Empirical ular Physical Elementary     Analysis No. R.sub.1 R.sub.2 R.sub.3 Y Y' formula weight constants Yield C      H N S       1 Me Me H Me H C.sub.8 H.sub.12 N.sub.2 O.sub.2 S 200 boiling 68.5%     calcu-      (B)        point:  lated: 48.00 6.00 14.00 16.00     112° C./  found: 48.09 6.07 14.14 15.98         0.008 mm Hg       melting         point:         33-34° C. 2 Et Et H Me H     C.sub.10 H.sub.16 N.sub.2 O.sub.2 S 228 boiling 55.8% calcu- (B)     point:  lated: 52.63 7.02 12.88 14.09         117° C./  found:     52.50 6.97 12.42 14.21         0.02 mm Hg         melting         point:             38-39° C. 3 Pr Pr H Me H C.sub.12 H.sub.20 N.sub.2     O.sub.2 S 256 boiling 85.7% calcu- (B)        point:  lated: 56.23 7.87     10.93         137° C./  found: 56.21 7.91 10.92         0.06 mm     Hg         n.sub.D.sup.25 : 1.5091 4 BuBu H Me H C.sub.14 H.sub.24     N.sub.2 O.sub.2 S 284 boiling 70.4% calcu- (B)        point:  lated:     59.15 8.45  9.86 11.27         104° C.  found: 59.09 8.42  9.37     11.36         molecular         distillation         n.sub.D.sup.25 :     1.5047 5 Me Pr H Me H C.sub.10 H.sub.16 N.sub.2 O.sub.2 S 228 boiling     77.3% calcu- (B)        point:  lated: 52.63 7.02 12.23         132.degre     e.      C./  found: 51.16 7.14 12.29         0.06 mm Hg         n.sub.D.sup.25     = 1.5185 6 Me iso Pr H Me H C.sub.10 H.sub.16 N.sub.2 O.sub.2 S 228     boiling 58.5% calcu- (B)        point:  lated: 52.63 7.02 12.28     116-113° C.  found: 51.66 7.07 12.26         0.05 mm Hg     n.sub.D.sup.25 : 1.5203 7 Me Bu H Me H C.sub.11 H.sub.18 N.sub.2 O.sub.2     S 242 boiling 75.9% calcu- (B)        point:  lated: 54.54 7.44 11.57          128° C./  found: 53.21 7.71 11.27         0.075 mm Hg      n.sub.D.sup.25 : 1.5142 8 Me sec H Me H C.sub.11 H.sub.18 N.sub.2     O.sub.2 S 242 boiling 80.7% calcu- (B)  Bu      point:  lated: 54.54     7.44 11.57         129° C./  found: 53.47 7.63 11.34     0.065 mm Hg         n.sub.25.sup.D : 1.5153 9 Et Bu H Me H C.sub.12     H.sub.20 N.sub.2 O.sub.2 S 256 boiling 65.3% calcu- (B)        point:     lated: 56.25 7.81 10.94         112-118° C.  found: 55.26 7.87     11.03         0.06 mm Hg         n.sub.D.sup.25 : 1.5097  10 iso iso H     Me H C.sub.12 H.sub.20 N.sub.2 O.sub.2 S 256 melting 92% calcu- (B) P Pr          point: of crude lated: 56.22 7.86 10.93 12.50         67-68°     C. product found: 56.08 7.92 10.93 12.49 11 iso iso H Me H C.sub.14     H.sub.24 N.sub.2 O.sub.2 S 284 boiling 84.5% calcu- (B) Bu Bu     point:  lated: 59.15 8.45  9.86         114-119° C.  found: 59.41     8.56  9.86         0.055 mm Hg         n.sub.25.sup.D : 1.5020 12 Et Et     H Et H C.sub.11 H.sub.18 N.sub.2 O.sub.2 S 242 boiling 68.9% calcu- (B)           point:  lated: 54.55 7.44 11.57 13.22         120°  C./     found: 54.59 7.47 11.51 13.30         0.02 mm Hg         n.sub.25.sup.D     : 1.5134 13 Pr Pr H Et H C.sub.13 H.sub.22 N.sub.2 O.sub.2 S 270 boiling     59.2% calcu- (B)        point:  lated: 57.78 8.15 10.37 11.85     120° C./  found: 58.04 7.88 10.35 11.98         0.013 mm Hg       n.sub.25.sup.D : 1.5066 14 iso iso H Et H C.sub.13 H.sub.22 N.sub.2     O.sub.2 S 270 boiling 79.2% calcu- (B) Pr Pr      point:  lated: 57.78     8.15 10.37         120° C./  found: 57.86 8.28 10.41         0.06     mm Hg         n.sub.25.sup.D : 1.5081 15 Pr Pr H Pr H C.sub.14 H.sub. 24     N.sub.2 O.sub.2 S 284 n.sub.25.sup.D : 1.5013 85.8% calcu- (B)     lated: 59.15 8.45  9.86 11.27           found: 59.08 8.56  9.89 11.38 16     iso iso H Pr H C.sub.14 H.sub.24 N.sub.2 O.sub.2 S 284 boiling 62%     calcu- (B) Pr Pr      point:  lated: 59.15 8.45      9.86         130° C./  found: 59.37 8.50 10.06         0.06 mm     Hg         n.sub.25.sup.D : 1.5038 17 Et Et H iso H C.sub.12 H.sub.20     N.sub.2 O.sub.2 S 256 boiling 38.3% calcu- (B)    Pr    point:  lated:     56.25 7.81 10.94 12.50         121° C./  found: 56.24 7.88 10.88     12.57         0.001 mm Hg         n.sub.25.sup.D : 1.5090 18 Pr Pr H iso     H C.sub.14 H.sub.24 N.sub.2 O.sub.2 S 284 boiling 50.6% calcu- (B)    Pr        point:  lated: 59.15 8.45  9.86 11.27         129-132° C./     found: 59.16 8.55 10.01 11.29         n.sub.25.sup.D : 1.5028 19 iso iso     H iso H C.sub.14 H.sub.24 N.sub.2 O.sub.2 S 284 boiling 66.5% calcu- (B)     Pr Pr  Pr    point:  lated: 59.15 8.45  9.86         123° C./     found: 59.10 8.48  9.92         0.06 mm Hg         n.sub.25.sup.D :     1.5030 20 Pr Pr H ter H C.sub.15 H.sub.26 N.sub.2 O.sub.2      S 298 n.sub.25.sup.D : 1.5013 90% calcu- (B)    Bu      lated: 60.40     8.72  9.40 10.74           found: 60.46 8.60  9.39 10.68 21 iso iso H     ter H C.sub.15 H.sub.26 N.sub.2 O.sub.2 S 298 boiling 75.8% calcu- (B)     Pr Pr  Bu    point:  lated: 60.40 8.72  9.40         122° C./     found: 60.36 8.68  9.91         0.06 mm Hg         n.sub.25.sup.D :     1.5003 22(B) Pr Pr H      ##STR14##      H C.sub.17 H.sub.22 N.sub.2 O.sub.2 S 318 n.sub.25.sup.D : 1.5663 86.7% c     alcu-lated:found: 64.1564.16 6.926.86  8.808.95 10.06 9.99 23(B) Et Et H      ##STR15##      H C.sub.15 H.sub.16 Cl.sub.2 N.sub.2 O.sub.2 S 359 n.sub.25.sup.D =     1.5885 87.4% calcu-lated:found: 50.1449.94 4.454.44  7.807.76  8.918.81     24(B) Pr Pr H      ##STR16##      H C.sub.17 H.sub.20 Cl.sub.2 N.sub.2 O.sub.2 S 387 n.sub.25.sup.D :     1.5706 90% calcu-lated:found: 52.7152.66 5.175.14  7.236.85  8.277.90 25     Et Et Me Me H C.sub.11 H.sub.18 N.sub.2 O.sub.2 S 242 boiling 56.2%     calcu- (B)        point:  lated: 54.50 7.44 11.57 13.22         118.degre     e. C./  found: 54.60 7.46 11.48 13.16         0.015 mm Hg     n.sub.25.sup.D : 1.5137 26 Pr Pr Me Me H C.sub.13 H.sub.22 N.sub.2     O.sub.2 S 270 boiling 30.6% calcu- (B)        point:  lated: 57.78 8.15     10.37 11.85         120° C./  found: 57.97 7.91 10.46 12.01       0.001 mm Hg         n.sub.25.sup.D : 1.5070 27 Pr Pr Me iso H C.sub.15     H.sub.26 N.sub.2 O.sub.2 S 298 boiling 57.7% calcu- (B)    Pr    point:     lated: 60.40 8.72  9.39         134-137° C.  found: 58.70 8.39     8.65         0.003 mm Hg         n.sub.25.sup.D : 1.5040 28 Et Et H Me     Cl C.sub.10 H.sub.15 ClN.sub.2 O.sub.2 S 262.5 boiling 66.9% calcu- (B)           point: 126° C./  lated: 45.71 5.71 10.67 12.15         0.06     mm Hg  found: 45.68 5.63 10.59 12.31         n.sub.25.sup.D : 1.5245 29     Pr Pr H Me Cl C.sub.12 H.sub.19 ClN.sub.2 O.sub.2 S 290.5 boiling 81.6%     calcu- (B)        point: 128° C./  lated: 49.57 6.54  9.64 11.01            0.045 mm Hg  found: 49.73 6.56  9.63 10.96         n.sub.25.sup.D     : 1.5154 30 Pr Pr H Me Br C.sub.12 H.sub.19 BrN.sub.2 O.sub.2 S 335     n.sub.25.sup.D : 1.5298 70% calcu- (B)          lated: 42.98 5.67  8.36     9.55           found: 43.07 5.70  8.32 9.60 31 Et Et H Et Cl C.sub.11     H.sub.17 ClN.sub.2 O.sub.2 S 276.5 boiling point: 81.8% calcu- (B)      120-123° C.  lated: 47.74 6.15 10.13 11.57         0.02 mm Hg     found: 47.70 6.19 10.07 11.60         n.sub.25.sup.D : 1.5196 32 Pr Pr H     Et Cl C.sub.13 H.sub.21 ClN.sub.2 O.sub.2 S 304.5 n.sub.25.sup.D :     1.5146 97.2% calcu- (B)          lated: 51.23 6.90  9.19 10.51     found: 51.12 7.05  9.18 10.60 33 Me Me Me Me Cl C.sub.9 H.sub.13     ClN.sub.2 O.sub.2 S 248.5 boiling point: 35.8% calcu- (B)     106-109° C.  lated: 43.46 5.23 11.27 12.88         0.03 mm Hg     found: 43.70 5.04 11.40 12.89         n.sub.25.sup.D : 1.5273 34 Et Et     Me Me Cl C.sub.11 H.sub.17 ClN.sub.2 O.sub.2 S 276.5 boiling point: 44%     calcu- (B)        114-119° C.  lated: 47.74 6.15 10.13 11.57        0.03 mm Hg  found: 47.73 6.12  9.98 11.56         n.sub.25.sup.D :     1.5214 35 Pr Pr MeMe Cl C.sub.13 H.sub.21 ClN.sub.2 O.sub.2 S 304.5     boiling point: 47.5% calcu- (B)        122-12° C.  lated: 51.23     6.90  9.19 10.51         0.016 mm Hg  found: 50.94 7.14  9.07 10.56        n.sub.25.sup.D : 5128 36 CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2 H Me     H C.sub.12 H.sub.16 N.sub.2 O.sub.2 S 252 boiling point: 71.2% calcu-     (B)        124° C./  lated: 57.14 6.35 11.11 12.70         0.011     mm Hg  found: 56.94 6.24 11.17 12.85         n.sub.25.sup.D : 1.5306 37     CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2 H iso H C.sub.14 H.sub.20     N2O.sub.2 S 280 boiling point: 54.7% calcu- (B)    Pr    132° C.     lated: 60.00 7.14 10.00 11.43         0.04 mm Hg  found: 59.85 7.09     10.09 11.56         n.sub.25.sup.D : 1.5210 38 CH.sub.2 CHCH.sub.2     CH.sub.2 CHCH.sub.2 Me Me H C.sub.13 H.sub.18 N.sub.2 O.sub.2 S 266     boiling point: 46.7% calcu- (B)        123-125  lated: 58.65 6.77 10.53     12.03         0.035 mm Hg  found: 58.73 6.39 10.60 12.17     n.sub.25.sup.D : 1.5273 39 CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2 H Et     Cl C.sub.13 H.sub.17 CH.sub.2 O.sub.2 S 300.5 n.sub.25.sup.D : 1.5320     88.8% calcu- (B)          lated: 51.91 5.66  9.32 10.65           found:     52.32 5.79  9.43 10.80 40 CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2 Me Me     Cl C.sub.13 H.sub.17 ClN.sub.2 O.sub.2 S 300.5 boiling point: 47.2%     calcu- (B)        123-127° C./  lated: 51.91 5.66  9.32 10.65         0.025 mm Hg  found: 51.90 5.68  9.37 10.68         n.sub.25.sup.D :     1.5295 41(B) H      ##STR17##      H Me H C.sub.12 H.sub.12 N.sub.2 O.sub.2 S 248 melting point:95°     C. 38.3% calcu-lated:found: 58.0658.14 4.844.89 11.2911.23 12.9012.84     heterocyclic structure              formed by  N, R.sub.1 and R.sub.2     42(B)      ##STR18##      H Me H C.sub.11 H.sub.16 N.sub.2 O.sub.2      S 240 melting point: 92.3° C. 92.3% calcu-lated: 55.00 6.67     11.67 13.33 43(B)      ##STR19##      H Me H C.sub.12 H.sub.18 N.sub.2 O.sub.2      S 254 boiling point: 160° C./0.05 mm Hgn.sub.25.sup.D : 1.5420     67.1% calcu-lated:found: 56.6956.64 7.097.06 11.0211.06 12.6012.65 44(B)      ##STR20##      H Et H C.sub.13 H.sub.20 N.sub.2 O.sub.2      S 268 boiling point:140° C./0.016 mm Hgn.sub.25.sup.D : 1.5368     62.8% calcu-lated:found: 58.2158.18 7.467.47 10.4510.39 11.9411.94 45(B)      ##STR21##      H Me H C.sub.10 H.sub.14 N.sub.2 O.sub.3      S 242 boiling point:150° C./0.01 mm Hgmelting point:61.5 30.7%     calcu-lated: found: 49.5949.59 5.785.61 11.57 11.60 13.2213.19

    __________________________________________________________________________    (Formula C)                                                                                               Molec-                                                                 Empirical                                                                            ular                                                                              Physical                                      No.                                                                              R.sub.1                                                                          R.sub.2                                                                              R.sub.3                                                                          Y Y' formula                                                                              weight                                                                            constants                                                                            Yield                                                                             Elementary analysis                __________________________________________________________________________                                                     C   H N                      46 Et Et     H  H H  C.sub.9 H.sub.14 N.sub.2 O.sub.2 S                                                   214 n.sub.25.sup.D : 1.5190                                                              91% calcu-                             (C)                                        lated:                                                                              50.47                                                                             6.54                                                                            13.08                                                             found:                                                                              49.89                                                                             6.63                                                                            12.75                                                                   C   H N    S                 47 Pr Pr     H  H H  C.sub.11 H.sub.18 N.sub.2 O.sub.2 S                                                  242 n.sub.25.sup.D : 1.5147                                                              83.4%                                                                             calcu-                             (C)                                        lated:                                                                              54.54                                                                             7.44                                                                            11.57                                                                              13.22                                                        found:                                                                              54.39                                                                             7.39                                                                            11.43                                                                              13.39                                                              C   H N                      48 Bu Bu     H  H H  C.sub.13 H.sub.22 N.sub.2 O.sub.2 S                                                  270 n.sub.25.sup.D : 1.5048                                                              99% calcu-                             (C)                                        lated:                                                                              57.78                                                                             8.15                                                                            10.37                                                             found:                                                                              57.58                                                                             8.07                                                                            10.23                  49 iso                                                                              iso    H  H H  C.sub.13 H.sub.22 N.sub.2 O.sub.2 S                                                  270 n.sub.25.sup.D : 1.5030                                                              96.3%                                                                             calcu-                             (C)                                                                              Bu Bu                                   lated:                                                                              57.78                                                                             8.15                                                                            10.37                                                             found:                                                                              56.56                                                                             8.18                                                                            10.22                  50 Et Bu     H  H H  C.sub.11 H.sub.18 N.sub.2 O.sub.2 S                                                  242 n.sub.25.sup.D : 1.5117                                                              97.9%                                                                             calcu-                             (C)                                        lated:                                                                              54.54                                                                             7.44                                                                            11.57                                                             found:                                                                              53.48                                                                             7.45                                                                            11.41                  51 iso                                                                              iso    H  H H  C.sub.11 H.sub.18 N.sub.2 O.sub.2 S                                                  242 n.sub.20.sup.D : 1.5130                                                              84.5%                                                                             calcu-                             (C)                                                                              Pr Pr                                   lated:                                                                              54.34                                                                             7.44                                                                            11.57                                                             found:                                                                              53.83                                                                             8.08                                                                            11.54                  52 Et Et     Me H H  C.sub.10 H.sub.16 N.sub.2 O.sub.2 S                                                  228 n.sub.25.sup.D : 1.5120                                                              33.9%                                                                             calcu-                             (C)                                        lated:                                                                              52.63                                                                             7.02                                                                            12.28                                                             found:                                                                              51.42                                                                             7.02                                                                            11.91                  53 Pr Pr     Me H H  C.sub.12 H.sub.20 N.sub.2 O.sub.2 S                                                  256 n.sub.25.sup.D : 1.5183                                                              30% calcu-                             (C)                                        lated:                                                                              56.25                                                                             7.81                                                                            10.94                                                             found:                                                                              55.34                                                                             7.84                                                                            10.96                  54 iso                                                                              iso    Me H H  C.sub.14 H.sub.24 N.sub.2 O.sub.2                                                    284 boiling point:                                                                       37.3%                                                                             calcu-                             (C)                                                                              Bu Bu                        100-109° C./                                                                      lated:                                                                              59.15                                                                             8.45                                                                            9.86                                                   0.015 mm Hg                                                                              found:                                                                              57.45                                                                             8.13                                                                            9.72                                                   n.sub.25.sup.D : 1.5075                       55 Et Et     H  H Me C.sub.10 H.sub.16 N.sub. 2 O.sub.2 S                                                 228 n.sub.25.sup.D : 1.5165                                                              96.8%                                                                             calcu-                             (C)                                        lated:                                                                              52.63                                                                             7.02                                                                            12.28                                                             found:                                                                              52.12                                                                             7.25                                                                            12.05                  56 Pr Pr     H  H Me C.sub.12 H.sub.20 N.sub.2 O.sub.2 S                                                  256 n.sub.25.sup.D : 1.5105                                                              98% calcu-                             (C)                                        lated:                                                                              56.25                                                                             7.81                                                                            10.94                                                             found:                                                                              56.36                                                                             7.98                                                                            10.78                  57 Bu Bu     H  H Me C.sub.14 H.sub.24 N.sub.2 O.sub.2 S                                                  284 n.sub.25.sup.D : 1.5041                                                              98.5%                                                                             calcu-                             (C)                                        lated:                                                                              59.15                                                                             8.45                                                                            9.86                                                              found:                                                                              58.00                                                                             8.40                                                                            9.70                   58 Et Bu     H  H Me C.sub.12 H.sub.20 N.sub.2 O.sub.2 S                                                  256 n.sub.25.sup.D : 1.5103                                                              98% calcu-                             C                                          lated:                                                                              56.25                                                                             7.81                                                                            10.94                                                             found:                                                                              55.64                                                                             7.82                                                                            10.94                  59 iso                                                                              iso    H  H Me C.sub.12 H.sub. 20 N.sub.2 O.sub.2 S                                                 256        75.8%                                                                             calcu-                             (C)                                                                              Pr Pr                                   lated:                                                                              56.25                                                                             7.81                                                                            10.94                                                             found:                                                                              54.80                                                                             7.76                                                                            10.92                  60 iso                                                                              iso    H  H Me C.sub.14 H.sub.24 N.sub.2 O.sub.2 S                                                  284 n.sub.25.sup.D : 1.5017                                                              74% calcu-                             (C)                                                                              Bu Bu                                   lated:                                                                              59.15                                                                             8.45                                                                            9.86                                                              found:                                                                              58.02                                                                             8.30                                                                            9.70                                                                    C   H N    S                 61 iso                                                                              iso    H  H H  C.sub.12 H.sub.20 N.sub.2 O.sub.2 S                                                  256 n.sub.D.sup.20 : 1.510                                                               87% calcu-                             (C)                                                                              Pr Bu                                   lated:                                                                              56.22                                                                             7.86                                                                            10.93                                                                              12.51                                                        found:                                                                              56.14                                                                             7.77                                                                            11.12                                                                              12.45             62 Pr sec    H  H H  C.sub.12 H.sub.20 N.sub.2 O.sub.2 S                                                  256 n.sub.D.sup.20 = 1.510                                                               85% calcu-                             (C)   Bu                                   lated:                                                                              56.22                                                                             7.86                                                                            10.93                                                                              12.51                                                        found:                                                                              56.29                                                                             7.74                                                                            11.03                                                                              12.75             63 Et iso    H  H H  C.sub.10 H.sub.16 N.sub.2 O.sub.2 S                                                  228 n.sub.D.sup.20 = 1.516                                                               44% calcu-                             C     Pr                                   lated:                                                                              52.61                                                                             7.06                                                                            12.27                                                                              14.04                                                        found:                                                                              52.32                                                                             7.01                                                                            12.10                                                                              14.22             64 (C)                                                                           Et                                                                                ##STR22##                                                                           H  H H  C.sub.13 H.sub.20 N.sub.2 O.sub.2 S                                                  268 n.sub.D.sup.20 = 1.534                                                               90% calcu-  lated: found:                                                                58.18 58.20                                                                       7.51 7.50                                                                       10.44 10.29                                                                        11.95 11.97      65 (C)                                                                           Me                                                                                ##STR23##                                                                           H  H H  C.sub.9 H.sub.14 N.sub.2 O.sub.3 S                                                   230 n.sub.D.sup.20 = 1.521                                                               68% calcu- lated: found:                                                                 46.94 46.55                                                                       6.13 6.09                                                                       12.16 12.09                                                                         13.92                                                                       14.17                                                              C   H N    S                 66 Et iso    H  H H  C.sub.11 H.sub.18 N.sub.2 O.sub.2 S                                                  242 n.sub.D.sup.20 = 1.510                                                               87% calcu-                             (C)   Bu                                   lated:                                                                              54.52                                                                             7.49                                                                            11.56                                                                              13.23                                                        found:                                                                              54.61                                                                             7.52                                                                            11.47                                                                              13.13             67 Me iso    H  H H  C.sub.10 H.sub.16 N.sub.2 O.sub.2 S                                                  228 n.sub.D.sup.20 = 1.515                                                               74% calcu-                             (C)   Bu                                   lated:                                                                              52.61                                                                             7.06                                                                            12.27                                                                              14.04                                                        found:                                                                              52.61                                                                             6.99                                                                            11.98                                                                              14.05                                                              C   H N                      68 iso                                                                              iso    H  H H  C.sub.11 H.sub.18 N.sub.2 O.sub.2 S                                                  242 n.sub.D.sup.20 = 1.513                                                               84.5%                                                                             calcu-                             (C)                                                                              Pr Pr                                   lated:                                                                              54.54                                                                             7.44                                                                            11.57                                                             found:                                                                              53.83                                                                             8.08                                                                            11.54                  __________________________________________________________________________

    __________________________________________________________________________     ##STR24##                                                                                         Molec-                                                                 Empirical                                                                            ular                                                                              Physical                                             No.                                                                              R.sub.1                                                                         R.sub.2                                                                         R.sub.3                                                                         Y  Y'                                                                              formula                                                                              weight                                                                            constants                                                                             Yield                                                                             Percentage analysis                      __________________________________________________________________________    69 Pr                                                                              Pr                                                                              H Me H C.sub.13 H.sub.22 N.sub.2 O.sub.2 S                                                  270 n.sub.25.sup.D = 1.5094                                                               87%     C  H  N  S                           (D)                                  calcu-                                                                        lated:                                                                            57.78                                                                            8.15                                                                             10.37                                                                            11.85                                                            found:                                                                            57.96                                                                            7.96                                                                             10.48                                                                            11.98                       __________________________________________________________________________     ##STR25##                                                                    __________________________________________________________________________    70 iso                                                                             iso                                                                             H Me H C.sub.13 H.sub.22 N.sub.2 O.sub.2 S                                                  270 n.sub.20.sup.D : 1.509                                                                83.5%   C  H  N  S                           (B)                                                                              Pr                                                                              Bu                              calcu-                                                                        lated:                                                                            57.75                                                                            8.20                                                                             10.36                                                                            11.86                                                            found:                                                                            57.68                                                                            8.18                                                                             10.42                                                                            11.69                       __________________________________________________________________________

EXAMPLE 4

Herbicidal activity in the pre-emergence treatment of crops in agreenhouse.

A number of seeds chosen in accordance with the plant species and thesize of the seed is sown in 9×9×9 ml pots filled with light agriculturalsoil.

The seeds are then covered with a layer of soil about 3 mm thick.

After moistening the soil, the pots are treated by spraying with anamount of liquor per pot which corresponds to a volume of 500 l/ha andcontains the active material in the dose in question.

The liquor is prepared by diluting, with water, an emulsifiableconcentrate having the following composition by weight:

active material to be tested: 20%

wetting and deflocculating agent: 10%

cyclohexanone (sovent): 70%

to the desired dilution, containing the active material in the dose inquestion. The tests were carried out at doeses of active materialranging from 1 kg/ha to 8 kg/ha.

The treated pots are then placed in troughs intended to receive thewatering water by sub-irrigation, and are kept for 35 days at ambienttemperature under 70% relative humidity.

After 35 days, the degree of destruction is determined relative to areference sample treated under the same conditions with a spraydispersion which does not contain the active material.

The plant species tested, both crops and weeds, were the following:

    ______________________________________                                        Graminaceous crops                                                            Wheat (Triticum vulgare)  WH                                                  Maize (Zea mays)          MA                                                  Rice (Oryza sativa)       RI                                                  Dicotyledonous crops                                                          Groundnuts (Arachis hypogea)                                                                            GR                                                  Rape (Brassica napus)     RA                                                  Cotton (Gossypium barbadenses)                                                                          CT                                                  Beans (Phaseolus vulgaris)                                                                              BE                                                  Soya (Glycine max)        SO                                                  Sunflower (Helianthus annuus)                                                                           SF                                                  Graminaceous weeds                                                            Wild oat (Avena fatua)    WO                                                  Crabgrass (Digitaria sanguinalis)                                                                       CG                                                  Panick grass (Echinochloa crus-galli)                                                                   PA                                                  Raygrass (Lolium multiflorum)                                                                           RA                                                  Foxtail (Setaria faberii) FX                                                  Slender foxtail (Alopecurus -myosuroides)                                                               SFX                                                 Dicotyledonous weeds                                                          Goosefoot (Chenopodium album)                                                                           GF                                                  Nightshade (Solanum nigrum)                                                                             NI                                                  Mustard (Sinapis arvensis)                                                                              MU                                                  Chickweed (Stellaria media)                                                                             CW                                                  ______________________________________                                    

The results found, which are recorded in the table below, are expressedas the percentage destruction of the treated plants relative to anuntreated reference sample.

The number 100 indicates that there is complete destruction of the plantin question. The results found are given in the table which follows:

    __________________________________________________________________________    Dose                    Dicotyledonous                                                                            Graminaceous                              in    Graminaceous weeds                                                                              weeds       crops    Dicotyledonous crops             No                                                                              kg/ha                                                                             WO CG PA RA FX SFX                                                                              GF NI MU CW WH MA RI GR RA CT BE SO SF                __________________________________________________________________________     2                                                                              4   60 -- 90 85 -- 95 0  -- 0  -- 15 0  70 -- 0  0  0  -- 0                   2   60 80 100                                                                              98 30 90 15 -- 0  0  10 0  80 0  10 0  0      0                                                                      0                        3                                                                              4   80 98 100                                                                              100                                                                              80 100                                                                              80 -- 10 50 80 0  95 0  25 0  0      0                                                                      0                         8   95 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              85 -- 20 80 100                                                                              0  100                                                                              0  30 0  0      0                                                                      20                       5                                                                              4   80 100                                                                              100                                                                              100                                                                              80 100                                                                              80 20 0  0  70 0  70 20 0  0  0      0                                                                      0                        6                                                                              4   50 80 100                                                                              90 25 95 50 30 0  60 30 0  0  0  0  0  0      5                                                                      0                        7                                                                              4   0  100                                                                              100                                                                              60 60 50 80 60 15 0  0  0  20 0  0  0  0      0                                                                      0                        8                                                                              4   20 100                                                                              100                                                                              90 20 90 60 90 0  0  60 0  60 0  0  0  0      0                                                                      0                        9                                                                              4   40 100                                                                              100                                                                              100                                                                              90 85 90 95 0  0  25 0  10 0  8  0  0      0                                                                      0                         1   70 0  100                                                                              100                                                                              50 98 10 -- 0  0  80 0  80 0  0  0  0      0                                                                      0                         2   80 50 100                                                                              100                                                                              85 100                                                                              15 -- 0  0  95 0  100                                                                              0  0  0  0      0                                                                      0                       10                                                                              4   100                                                                              98 100                                                                              100                                                                              98 100                                                                              50 -- 0  10 98 0  100                                                                              0  0  0  0      10                                                                     0                         8   100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              85 -- 0  60 98 5  100                                                                              0  10 0  30     25                                                                     10                      11                                                                              4   70 100                                                                              100                                                                              90 60 90 25 100                                                                              0  100                                                                              10 0  0  0  0  0  0      0                                                                      0                       13                                                                              4   60 100                                                                              100                                                                              98 98 85 60 -- 80 70 0  0  80 -- 0  0  0      --                                                                     0                         1   40 90 100                                                                              100                                                                              80 100                                                                              0  50 0  0  50 0  95 0  0  0  0      0                                                                      0                         2   60 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              80 80 0  0  90 0  100                                                                              0  0  0  0      0                                                                      0                       14                                                                              4   95 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              98 0  60 100                                                                              0  100                                                                              10 0  0  0      0                                                                      0                         8   100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              0  100                                                                              100                                                                              0  100                                                                              20 0  0  30     0                                                                      10                      15                                                                              4   20 100                                                                              100                                                                              98 100                                                                              98 80 15 0  25 0  0  80 -- -- 0  0      0                                                                      0                         2   60 100                                                                              100                                                                              98 90 98 60 60 0  20 30 0  98 0  0  0  0      0                                                                      0                       16                                                                              4   70 100                                                                              100                                                                              100                                                                              95 100                                                                              100                                                                              100                                                                              0  60 40 0  100                                                                              0  0  0  0      0                                                                      0                         8   85 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              0  85 60 0  100                                                                              30 0  0  0      0                                                                      0                       17                                                                              4   65 100                                                                              90 90 95 50 0  0  0  0  -- -- -- -- -- -- --     --                                                                     --                      18                                                                              4   50 100                                                                              100                                                                              98 98 90 60 5  5  0  60 0  -- -- 0  -- --     --                                                                     --                        2   40 100                                                                              100                                                                              100                                                                              100                                                                              98 80 90 0  10 40 0  100                                                                              0  0  0  0      0                                                                      0                       19                                                                              4   80 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              90 100                                                                              0  40 80 0  100                                                                              0  0  0  30     0                                                                      0                         8   100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              0  80 100                                                                              0  100                                                                              60 0  10 60     25                                                                     0                       20                                                                              4   10 100                                                                              98 95 95 90 20 0  0  0  0  0  15 -- 0  0  0      0                                                                      0                       22                                                                              4   0  100                                                                              10 60 60 70 0  0  0  0  0  0  0  -- 0  0  0      0                                                                      0                       26                                                                              4   85 -- 85 95 -- 85 90 -- 5  50 0  0  10 -- 0  0  0      --                                                                     0                       29                                                                              4   60 100                                                                              98 85 80 90 10 5  0  0  20 0  -- -- 0  -- --     --                                                                     --                      30                                                                              4   10 -- 98 85 -- 95 0  -- 10 0  0  0  0  -- 0  0  0      --                                                                     0                       31                                                                              4   90 95 100                                                                              95 95 90 5  0  0  0  30 0  -- -- 0  -- --     --                                                                     --                      32                                                                              4   40 100                                                                              100                                                                              60 95 80 5  5  0  0  25 0  -- -- 0  -- --     --                                                                     --                      33                                                                              4   10 25 10 80 85 90 0  0  0  0  0  0  50 -- 0  0  0      0                                                                      0                       34                                                                              4   80 95 90 98 95 95 30 0  0  15 30 0  -- -- 0  -- --     --                                                                     --                      35                                                                              4   90 100                                                                              85 90 95 85 25 5  0  0  25 0  -- -- 0  -- --     --                                                                     --                      36                                                                              4   15 -- 60 60 -- 80 0  -- 0  -- 0  0  25 -- 0  0  0      --                                                                     0                       37                                                                              4   30 100                                                                              95 70 50 50 5  0  0  0  -- -- -- -- -- -- --     --                                                                     --                      38                                                                              4   15 80 60 20 30 70 0  0  0  0  -- -- -- -- -- -- --     --                                                                     --                      39                                                                              4   5  95 70 50 15 70 0  0  0  0  -- -- -- -- -- -- --     --                                                                     --                      40                                                                              4   80 98 25 15 5  40 0  0  0  0  0  0  -- -- 0  -- --     --                                                                     --                      43                                                                              4   0  -- 80 80 -- 70 30 -- 0  0  10 0  0  -- 0  0  0      --                                                                     0                       44                                                                              4   0  -- 80 85 -- 85 30 -- 0  0  10 0  15 -- 0  0  0      --                                                                     5                       46                                                                              4   80 100                                                                              100                                                                              100                                                                              50 100                                                                              50 80 0  0  10 0  15 0  10 0  0      10                                                                     0                         2   100                                                                              100                                                                              100                                                                              100                                                                              20 100                                                                              -- 100                                                                              0  80 10 0  25 0  10 0  0      0                                                                      0                       47                                                                              4   100                                                                              100                                                                              100                                                                              100                                                                              40 100                                                                              -- 100                                                                              0  85 20 0  60 0  15 0  0      40                                                                     0                         8   100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              30 95 30 0  90 0  25 10 0      60                                                                     100                       2   80 98 98 80 0  25 -- 90 0  0  0  0  0  0  0  0  0      0                                                                      0                       48                                                                              4   90 100                                                                              100                                                                              95 26 70    100                                                                              0  0  0  0  0  0  10 0  0      0                                                                      0                         8   100                                                                              100                                                                              100                                                                              100                                                                              50 90 -- 100                                                                              15 90 0  0  10 0  20 0  0      0                                                                      0                       49                                                                              4   95 100                                                                              95 50 50 100                                                                              30 80 10 100                                                                              5  0  0  0  0  0  0      0                                                                      0                         2   90 100                                                                              100                                                                              100                                                                              85 90 0  80 0  0  10 0  0  0  0  0  0      0                                                                      0                       50                                                                              4   100                                                                              100                                                                              100                                                                              100                                                                              90 100                                                                              50 90 25 30 10 0  60 0  10 0  0      0                                                                      0                         8   100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              70 100                                                                              80 70 15 0  95 0  40 0  0      0                                                                      10                      51                                                                              4   100                                                                              95 100                                                                              100                                                                              15 100                                                                              0  95 0  0  90 0  15 0  0  15 0      0                                                                      0                       52                                                                              4   95 100                                                                              98 100                                                                              30 100                                                                              0  0  0  0  15 0  40 0  0  10 0      0                                                                      0                       53                                                                              4   100                                                                              100                                                                              100                                                                              95 20 100                                                                              80 100                                                                              0  100                                                                              30 0  0  0  10 0  0      0                                                                      0                       54                                                                              4   90 90 70 85 5  90 0  30 0  10 0  0  0  30 0  0  0      5                                                                      0                       55                                                                              4   60 100                                                                              100                                                                              100                                                                              80 100                                                                              60 0  10 50 80 10 80 0  0  0  0      0                                                                      0                         2   15 100                                                                              100                                                                              95 80 90 -- 100                                                                              0  80 15 0  0  0  10 0  0      0                                                                      0                       56                                                                              4   30 100                                                                              100                                                                              100                                                                              95 100                                                                              -- 100                                                                              20 95 20 0  20 0  15 0  0      0                                                                      0                         8   98 100                                                                              100                                                                              100                                                                              98 100                                                                              -- 100                                                                              60 100                                                                              40 0  50 10 50 0  0      20                                                                     0                       57                                                                              4   25 100                                                                              90 80 10 60 20 90 0  10 0  0  0  0  0  0  0      0                                                                      0                         2   10 80 98 90 80 60 -- 100                                                                              0  80 10 0  0  0  15 0  0      0                                                                      0                       58                                                                              4   30 100                                                                              100                                                                              100                                                                              90 90 -- 100                                                                              20 90 25 0  5  0  30 0  0      0                                                                      0                         8   80 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              50 100                                                                              60 0  15 25 50 0  50     50                                                                     30                      59                                                                              4   60 100                                                                              100                                                                              100                                                                              80 100                                                                              80 90 0  60 80 0  80 0  0  0  0      0                                                                      0                         2   10 90 90 60 80 85 0  100                                                                              0  90 0  0  0  0  0  0  0      0                                                                      0                       60                                                                              4   40 100                                                                              100                                                                              90 85 90 0  100                                                                              0  100                                                                              0  0  0  0  5  0  0      0                                                                      0                         8   85 100                                                                              100                                                                              98 100                                                                              100                                                                              50 100                                                                              0  100                                                                              15 0  0  0  15 0  0      0                                                                      0                       61                                                                              1   100                                                                              100                                                                              100                                                                              100                                                                              85 100                                                                              30 0  0  0  30 0  100                                                                              0  0  0  0      0                                                                      0                         4   100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              80 30 0  60 80 0  100                                                                              0  0  0  0      0                                                                      0                       62                                                                              1   85 100                                                                              100                                                                              100                                                                              80 100                                                                              10 10 0  0  30 0  70 0  0  0  0      0                                                                      0                         4   100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              80 40 10 30 50 0  100                                                                              0  0  0  0      30                                                                     0                       63                                                                              4   100                                                                              100                                                                              100                                                                              100                                                                              70 100                                                                              70 10 0  0  90 0  95 0  0  10 0      0                                                                      0                       64                                                                              4   90 100                                                                              100                                                                              100                                                                              30 100                                                                              70 0  0  0  0  0  25 0  0  0  0      0                                                                      10                      66                                                                              4   100                                                                              100                                                                              100                                                                              100                                                                              80 100                                                                              80 80 0  60 60 0  90 15 0  0  0      0                                                                      0                       67                                                                              4   100                                                                              100                                                                              100                                                                              100                                                                              50 100                                                                              60 0  0  0  0  0  50 0  0  0  0      0                                                                      0                       68                                                                              4   100                                                                              95 100                                                                              100                                                                              15 100                                                                              0  95 0  0  90 0  15 0  0  15 0      0                                                                      0                       69                                                                              4   90 100                                                                              100                                                                              100                                                                              90 90 60 20 0  70 0  0  20 -- 0  0  0      20                                                                     0                       70                                                                              4   100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              90 20 0  85 85 0  100                                                                              0  0  0  0      0                                                                      0                       __________________________________________________________________________

These results show the good herbicidal action of the compounds accordingto the invention and their selectivity regarding the crops when they areapplied before emergence or before sowing of the crops. In general, allof these compounds have a good herbicidal action on graminaceous weeds.Some of the compounds are also active on certain dicotyledonous weeds.

Particularly valuable results have been obtained in the case of thefollowing compounds:

Compound no. 10: 3-methyl-isoxazol-5-yl-methylN,N-diisopropyl-thiolcarbamate.

Compound no. 14: 3-ethyl-isoxazol-5-yl-methylN,N-diisopropylthiolcarbamate.

Compound no. 47: isoxazol-3-yl-methyl N,N-di-(n-propyl)-thiolcarbamate.

Compound no. 3: 3-methyl-isoxazol-5-methylN,N-di-(n-propyl)-thiolcarbamate.

Compound no. 16: 3-(n-propyl)-isoxazol-5-yl-methylN,N-diisopropylthiolcarbamate.

Compound no. 19: 3-isopropyl-isoxazol-5-yl-methylN,N-diisopropylthiolcarbamate.

Compound no. 50: isoxazol-3-yl-methyl N-ethyl-N-butyl-thiolcarbamate.

Compound no. 56: 5-methyl-isoxazol-3-yl-methylN,N-di-(n-propyl)-thiolcarbamate.

Compound no. 60: 5-methyl-isoxazol-3-yl-methylN,N-diisobutylthiolcarbamate.

Compound no. 61: isoxazol-3-yl-methylN-isopropyl-N-isobutylthiolcarbamate.

Compound no. 62: isoxazol--3-yl-methylN-propyl-N-sec.-butylthiolcarbamate.

Compound no. 63: isoxazol-3-yl-methylN-methyl-N-isopropylthiolcarbamate.

Compound no. 70: 3-methyl-isoxazol-5-yl-methylN-isopropyl-N-isobutyl-thiolcarbamate.

Thus, by way of example, at doses from 2 kg./ha., compound no. 14effects 100% destruction of crabgrass, panickgrass raygrass, foxtail andslender foxtail, wild oat being a little less sensitive. At this samedose, it also destroys certain dicotyledonous weeds, such as goosefootand nightshade. At a dose of 4 kg./ha., the compound is well toleratedby crops of maize, rape, cotton and sunflower.

For herbicidal treatment by means of the compounds according to theinvention, the dose of active material to be used can vary from 0.5 to10 kg./ha., depending on the compound used, the type of crop and thenature of the soil. Preferably, this dose is between about 1 kg./ha. and4 kg./ha.

For use in practice, the compounds according to the invention are rarelyemployed alone. Most frequently, they form part of formulations which ingeneral comprise a carrier and/or a surface-active agent acceptable tothe plants, in addition to the active material according to theinvention.

The term "carrier" in the sense of the present description denotes anorganic or inorganic, natural or synthetic material with which theactive material is associated in order to facilitate its application tothe plant, to the seeds or to the soil, or to facilitate its transportor its handling. The carrier can be solid (clays, natural or syntheticsilicates, resins, waxes, solid fertilisers and the like) or fluid(water, alcohols, ketones, petroleum fractions, chlorinated hydrocarbonsand liquified gases).

The surface-active agent can be an emulsifier, dispersing agent orwetting agent, and each of these can be ionic or non-ionic. Exampleswhich may be mentioned are salts of polyacrylic acids and ofligninsulphonic acids, and condensates of ethylene oxide with fattyalcohols, fatty acids or fatty amines.

The compositions according to the invention can be prepared in the formof wettable powders, dusting powders, granules, solutions, emulsifiableconcentrates, emulsions, suspension concentrates and aerosols.

The wettable powders are usually prepared in such a way that theycontain from 25 to 95% by weight of active material and they usuallycontain, in addition to a solid carrier, from 0 to 5% by weight of awetting agent and from 3 to 10% by weight of one or more stabilizersand/or other additives, such as penetrating agents, adhesives oranti-caking agents, dyestuffs and the like. By way of example, thefollowing is the composition of a wettable powder.

active material (compound no. 47): 50%

calcium lignosulphate (deflocculating agent): 5%

anionic wetting agent: 1%

anti-caking silica: 5%

kaolin (extender): 39%

The water-soluble powders are obtained by mixing from 20 to 95% byweight of active material, from 0 to 10% of an anti-caking extender andfrom 0 to 1% of a wetting agent, the remainder consisting of awater-soluble extender, principally a salt.

The following is an example of the composition of a water-solublepowder:

active material (compound no. 50): 70%

anionic wetting agent: 0.5%

anti-caking silica: 5%

sodium sulphate (soluble extender): 24.5%

The granules, which are intended to be put on the soil, are usuallyprepared in such a way that they between 0.1 and 2 mm in size, and theycan be manufactured by agglomeration or impregnation. In general, thegranules contain from 0.5 to 25% of active material and from 0 to 10% byweight of additives, such as stabilizers, slow-liberation modifiers,binders and solvents.

The emulsifiable concentrates which can be applied by spraying usuallycontain, in addition to the solvent and, where necessary, a co-solvent,from 10 to 50% by weight/volume of active material and from 2 to 20% byweight/volume of appropriate additives, such as stabilizers, penetratingagents, corrosion inhibitors, dyestuffs and adhesives.

By way of example, the following is the composition of an emulsifiableconcentrate, the amounts being expressed in g./liter:

active material (compound no. 60): 400 g/l

alkali metal dodecylbenzenesulphonate: 24 g/l

nonylphenol reacted with 10 molecules of ethylene oxide: 16 g/l

cyclohexanone: 200 g/l

aromatic solvent: q.s.p. 1 liter

The suspension concentrates, which can also be applied by spraying, areprepared in such a way that a stable fluid product which does not settleout is obtaned, and they usually contain from 10 to 75% by weight ofactive material, from 0.5 to 15% by weight of surface-active agents,from 0.1 to 10% by weight of thixotropic agents, from 0 to 10% by weightof appropriate additives, such as anti-foaming agents, corrosioninhibitors, stabilizers, penetrating agents and adhesives, and, as acarrier, water or an organic liquid in which the active material issubstantially insoluble: certain organic solid materials or inorganicsalts can be dissolved in the carrier to assist in preventingsedimentation or to act as anti-freeze agents for the water.

Aqueous dispersions and aqueous emulsions, for example compositionsobtained by diluting a wettable powder or an emulsifiable concentrateaccording to the invention with water, fall within the general scope ofthe present invention. The emulsions can be of the water-in-oil type orof the oil-in-water type and they can have a thick consistency such asthat of a "mayonnaise".

The compositions according to the invention can contain otheringredients, for example protective colloids, adhesives or thickeners,thixotropic agents, stabilizers or sequestering agents, as well as otherknown active material possessing pesticidal properties, in particularpossessing insecticidal or fungicidal properties.

We claim:
 1. A compound of the formula: ##STR26## in which R₁ and R₂ areidentical or different and each represents a linear or Branched alkylradical containing 1 to 4 carbon atoms, cyclohexyl or methoxyethyl, R₃is a hydrogen atom or methyl group and Y and Y' are identical ordifferent and each represents a hydrogen or methyl group.
 2. A compoundaccording to claim 1, in which said thiolcarbamate is chosen from thegroup comprising: isoxazol-3-yl-methyl N,N-di-(n-propyl)-thiolcarbamate,isoxazol-3-yl-methyl N-ethyl-N-butyl-thiolcarbamate,5-methyl-isoxazol-3-yl-methyl N,N-di-(n-propyl)-thiolcarbamate,5-methyl-isoxazol-3-yl-methyl N,N-diisobutyl-thiolcarbamate,isoxazol-3-yl-methyl N-isopropyl-N-isobutyl-thiolcarbamate,isoxazol-3-yl-methyl N-propyl-N-sec.-butyl-thiolcarbamate andisoxazol-3-yl-methyl N-ethyl-N-isopropyl-thiolcarbamate.
 3. A compoundwhich is 3-methyl-isoxazol-4-yl-methyl N,N-di-propyl-thiolcarbamate. 4.A herbicidal composition comprising as the active material, at least onecompound according to any of claims 1, 2 or 3 in an herbicidallyeffective amount in combination with inert an agriculturally acceptablecarrier and/or agriculturally acceptable surface active agent.
 5. Acomposition according to claim 4, in which said composition containssaid active material in an amount of between 0.5 and 95% by weight andin which the composition contains at least one inert agriculturallyacceptable carrier and/or surface-active agent.
 6. Process for theselective destruction of weeds in a crop of maize, groundnuts, rape,cotton, beans, soya, sunflowers, wheat or rice which comprises applyingto the locus of said crop before emergence or before sowing said crop anherbicidally effective amount of a composition according to claim 4.